CN113921768A - Preparation method of flexible self-supporting iron-doped porous carbon nanofiber lithium metal negative electrode framework material - Google Patents
Preparation method of flexible self-supporting iron-doped porous carbon nanofiber lithium metal negative electrode framework material Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 23
- 239000002133 porous carbon nanofiber Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 14
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 13
- 239000002121 nanofiber Substances 0.000 claims abstract description 9
- 238000000151 deposition Methods 0.000 claims abstract description 7
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 7
- 230000005684 electric field Effects 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- 238000009987 spinning Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 11
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- 239000002904 solvent Substances 0.000 claims description 7
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- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000007747 plating Methods 0.000 claims description 3
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical group CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 2
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- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
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- 238000010899 nucleation Methods 0.000 abstract description 2
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- 239000001301 oxygen Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical group COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
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- 210000004027 cell Anatomy 0.000 description 2
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- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- HNCXPJFPCAYUGJ-UHFFFAOYSA-N dilithium bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].[Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F HNCXPJFPCAYUGJ-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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Abstract
The invention discloses a preparation method of a flexible self-supporting iron-doped porous carbon nanofiber lithium metal negative electrode framework material, and belongs to the field of lithium metal battery materials. The nanofiber is prepared from cheap iron acetylacetonate, polyacrylonitrile and polymethyl methacrylate as raw materials through electrostatic spinning and high-temperature heat treatment. The lithium metal negative electrode framework prepared by the invention has larger specific surface area, can make an electric field uniform and reduce local current density, thereby causing uniform lithium deposition and effectively avoiding the formation of lithium dendrites; the three-dimensional porous body can provide open pores to adapt to volume change and lithium ion transmission; the nitrogen and oxygen doped carbon body can generate strong interaction with lithium atoms, so that lithium nucleation becomes easier and more uniform; meanwhile, the preparation method of the material is simple, low in cost, green, efficient, and capable of realizing large-scale production, and the material can be used as an ideal high-performance lithium metal negative electrode framework material and has a good practical prospect.
Description
Technical Field
The invention relates to a preparation method of a flexible self-supporting iron-doped porous carbon nanofiber lithium metal negative electrode framework material, and belongs to the field of lithium metal battery materials.
Background
With the rapid development of mobile phones, notebook computers and electric vehicles, widely used lithium ion batteries have met with a number of difficulties in meeting the ever-increasing demands for energy storage systems with high energy density and long cycle life. Lithium metal negative electrodes due to their high theoretical specific capacity (3860mAh g)-1) Low reaction potential (-3.04V, relative to standard hydrogen electrodes) and light weight, have long been recognized as "holy grail" in the electrode materials of the next generation lithium batteries. However, lithium metal batteries have a serious problem of lithium dendrite growth, which has not been able to be industrialized until late.
The growth of lithium dendrites tends to cause a series of problems. When the dendrite pierces the separator and comes into contact with the positive electrode, a short circuit of the battery is caused, which causes a safety problem. A reaction between lithium metal and electrolyte occurs, irreversibly consuming the active lithium metal material and electrolyte, drastically reducing coulombic efficiency. During the circulation process, dendritic lithium can fall off from the lithium sheet to form a 'dead lithium' layer, which not only reduces the coulombic efficiency, but also increases the internal resistance of the battery and influences the circulation performance. For lithium metal anodes, the volume change during each plating/stripping process is infinite. Effectively inhibit the growth of dendrites and prolong the cycle life of the battery, which is the most urgent task in the practical application of the lithium metal battery.
Since the 21 st century, researchers have adopted various processes to develop lithium metal negative electrode framework materials that can suppress the growth of lithium dendrites and withstand large volume changes. The method of appropriate solid electrolyte interface film design, electrolyte composition optimization, structural design of the metallic lithium negative electrode and the like provides a good solution for the problem of lithium dendrite growth. Among them, the structural design of the lithium metal negative electrode is a focus of research. By the structural design of the metallic lithium negative electrode, the volume expansion can be reduced, and the current density can be reduced, so that the growth of lithium dendrites is inhibited, and the performance of the lithium metal battery is improved.
Disclosure of Invention
The invention aims to provide a preparation method of a flexible self-supporting iron-doped porous carbon nanofiber lithium metal negative electrode framework material, which is used for solving the problems of the traditional lithium metal negative electrode and providing a certain technical guarantee for the commercial production of a lithium metal battery.
The invention provides a preparation method of a flexible self-supporting iron-doped porous carbon nanofiber lithium metal negative electrode framework material, which adopts the following specific preparation process:
(1) the polymer is selected from Polyacrylonitrile (PAN) and polymethyl methacrylate (PMMA), and the metal salt is ferric acetylacetonate (Fe (C)5H7O2)3) The solvent is N, N-Dimethylformamide (DMF). Firstly Fe (C)5H7O2)3Dissolving in DMF, adding PAN and PMMA, placing in water bath at 50 deg.C, magnetically stirring for 12h, and mixing to obtain PAN/PMMA/Fe (C)5H7O2)3DMF spinning solution.
(2) The method adopts a solution electrostatic spinning method, the spinning solution is filled into a medical injector, a rotary receiver is connected with a positive voltage direct current power supply, a needle head is connected with a negative voltage direct current power supply, a micro-injection pump is started to push the spinning solution to advance, the spinning solution is stretched under the action of an electric field force, a solvent is volatilized, and a precursor nanofiber membrane is obtained on the rotary receiver. The specific parameters of the electrostatic spinning process are as follows: the positive pressure is 10kV, the negative pressure is 8kV, the propelling speed is 0.5ml/h, the receiving distance is 12cm, the rotating speed of the rotary receiver is 900r/min, the ambient temperature is 20 ℃, and the ambient humidity is 20-30%.
(3) And placing the obtained precursor nanofiber membrane in a vacuum tube furnace for high-temperature heat treatment. Firstly, placing the mixture in air for pre-oxidation at 250 ℃ for 2h at a heating rate of 1 ℃/min. Then, high-temperature sintering is carried out in a nitrogen atmosphere, the sintering temperature is 800 ℃, the time is 1h, and the heating rate is 3 ℃/min.
And (3) forming the flexible self-supporting iron-doped porous carbon nanofiber material and lithium metal into a half-cell, and plating lithium in the framework material by a deposition method to obtain the lithium metal battery composite cathode.
The invention provides a preparation method of a flexible self-supporting iron-doped porous carbon nanofiber lithium metal negative electrode framework material. The three-dimensional porous framework material has a large specific surface area, so that an electric field is uniform, and the local current density is reduced, thereby causing uniform lithium deposition; the three-dimensional porous body can provide open pores to adapt to volume change and lithium ion transmission; the nitrogen and oxygen doped carbon body can generate strong interaction with lithium atoms, so that lithium nucleation becomes easier and more uniform; the high conductivity surface reduces the lithium ion deposition overpotential and improves the coulombic efficiency; meanwhile, the preparation method of the material is simple, low in cost, green, efficient and easy for large-scale production, and the material can be used as an ideal high-performance lithium metal negative electrode framework material and has a good practical prospect.
Drawings
FIG. 1 is an SEM image of flexible self-supported iron-doped porous carbon nanofiber prepared in example 2 of the invention
FIG. 2 is a time-voltage curve diagram of the flexible self-supported iron-doped porous carbon nanofiber prepared in example 2 of the present invention
FIG. 3 shows the coulomb efficiency test result of the flexible self-supported iron-doped porous carbon nanofiber prepared in example 2 of the present invention
Detailed Description
In order to explain the preparation method of the flexible self-supporting iron-doped porous carbon nanofiber lithium metal negative electrode framework material of the invention more fully, the following specific examples of the preparation method are provided, but the invention is not limited to the examples.
Example 1:
(1) 0.4g of iron acetylacetonate (Fe (C)) was weighed out5H7O2)3) Dissolved in 4.4g of N, N-Dimethylformamide (DMF), followed by addition of 0.6g of Polyacrylonitrile (PAN) and 0.04g of polymethyl methacrylate (PMMA), and the resulting solution was magnetically stirred in a water bath at 50 ℃ for 12 hours to form a uniform spinning solution.
(2) The prepared spinning solution is sucked into a medical injector by adopting a solution electrostatic spinning method, a rotary receiver is connected with positive pressure of 10kV, a needle head is connected with negative pressure of 8kV, a micro-injection pump is started to propel the spinning solution to advance at the speed of 0.5ml/h, the spinning solution is stretched under the action of electric field force, a solvent is volatilized, a precursor nanofiber membrane is obtained on the rotary receiver with the rotating speed of 900r/min, and the distance between the needle head and the rotary receiver is 12 cm. Wherein the environmental parameters are specifically: the temperature is 20 ℃, and the environmental humidity is 20-30%.
(3) And placing the obtained precursor nanofiber membrane in a vacuum tube furnace for high-temperature heat treatment. Firstly, placing the mixture in air for pre-oxidation at 250 ℃ for 2h at a heating rate of 1 ℃/min. And then, performing high-temperature sintering in a nitrogen atmosphere, wherein the sintering temperature is 800 ℃, the time is 1h, and the heating rate is 3 ℃/min, so as to obtain the flexible self-supporting iron-doped porous carbon nanofiber.
Example 2:
(1) 0.6g of iron acetylacetonate (Fe (C)) was weighed out5H7O2)3) Dissolved in 4.4g of N, N-Dimethylformamide (DMF), followed by addition of 0.6g of Polyacrylonitrile (PAN) and 0.04g of polymethyl methacrylate (PMMA), and the resulting solution was magnetically stirred in a water bath at 50 ℃ for 12 hours to form a uniform spinning solution.
(2) The prepared spinning solution is sucked into a medical injector by adopting a solution electrostatic spinning method, a rotary receiver is connected with positive pressure of 10kV, a needle head is connected with negative pressure of 8kV, a micro-injection pump is started to propel the spinning solution to advance at the speed of 0.5ml/h, the spinning solution is stretched under the action of electric field force, a solvent is volatilized, a precursor nanofiber membrane is obtained on the rotary receiver with the rotating speed of 900r/min, and the distance between the needle head and the rotary receiver is 12 cm. Wherein the environmental parameters are specifically: the temperature is 20 ℃, and the environmental humidity is 20-30%.
(3) And placing the obtained precursor nanofiber membrane in a vacuum tube furnace for high-temperature heat treatment. Firstly, placing the mixture in air for pre-oxidation at 250 ℃ for 2h at a heating rate of 1 ℃/min. And then, performing high-temperature sintering in a nitrogen atmosphere, wherein the sintering temperature is 800 ℃, the time is 1h, and the heating rate is 3 ℃/min, so as to obtain the flexible self-supporting iron-doped porous carbon nanofiber.
SEM test characterization is carried out on the flexible self-supporting iron-doped porous carbon nanofiber prepared in the above way, and results show that iron nanoparticles are uniformly dispersed on the surface of the carbon nanofiber, as shown in FIG. 1. As the pore-forming component PMMA is decomposed, a small amount of tubular pore canals with different sizes are formed inside the carbon nano-fiber.
The prepared flexible self-supporting iron-doped porous carbon nanofiber is compounded with lithium to be used as a positive electrode material, metal lithium is used as a negative electrode, 1.0M bis (trifluoromethanesulfonimide) Lithium (LiTFSI) and 0.2M LiNO3 solution (the solvent is ethylene glycol dimethyl ether (DME) and 1, 3-Dioxolane (DOL) and the volume ratio is 1:1) are used as electrolyte, and a diaphragm is formed into a half cell by adopting Celgard 2325.
The charged battery was charged at a rate of 1mA/cm2Current density of 0.5mAh/cm2The half cells were subjected to charge-discharge cycling tests for deposition capacity and the results are shown in fig. 2. The half-cell using iron-doped porous carbon nanofibers showed a lower overpotential (11mV), which remained stable over 420 cycles.
The charged battery was charged at a rate of 1mA/cm2Current density of 1mAh/cm2For the deposition of capacity, a charge-discharge cycle test was carried out on the half-cell at a charge voltage of 1V, and the resultsAs shown in fig. 3. Half-cells using iron-doped porous carbon nanofibers were able to stabilize over 190 cycles with coulombic efficiency above 98%, while half-cells using carbon nanofibers started to decay in coulombic efficiency after 120 cycles.
Claims (1)
1. A flexible self-supporting iron-doped porous carbon nanofiber lithium metal negative electrode framework material and a preparation method thereof are characterized by comprising the following specific steps:
(1) the polymer is selected from Polyacrylonitrile (PAN) and polymethyl methacrylate (PMMA), and the metal salt is ferric acetylacetonate (Fe (C)5H7O2)3) The solvent is N, N-Dimethylformamide (DMF); firstly Fe (C)5H7O2)3Dissolving in DMF, adding PAN and PMMA, placing in water bath at 50 deg.C, magnetically stirring for 12h, and mixing to obtain PAN/PMMA/Fe (C)5H7O2)3A DMF spinning solution;
(2) the method of solution electrostatic spinning is adopted, the spinning solution is filled into a medical injector, a rotary receiver is connected with a positive voltage direct current power supply, a needle head is connected with a negative voltage direct current power supply, a micro-injection pump is started to push the spinning solution to advance, the spinning solution is stretched under the action of an electric field force, a solvent is volatilized, and a precursor nanofiber membrane is obtained on the rotary receiver; the specific parameters of the electrostatic spinning process are as follows: the positive pressure is 10kV, the negative pressure is 8kV, the propelling speed is 0.5ml/h, the receiving distance is 12cm, the rotating speed of the rotary receiver is 900r/min, the ambient temperature is 20 ℃, and the ambient humidity is 20-30%;
(3) placing the obtained precursor nanofiber membrane in a vacuum tube furnace for high-temperature heat treatment; firstly, placing the mixture in air for pre-oxidation at 250 ℃ for 2h at a heating rate of 1 ℃/min; then, high-temperature sintering is carried out in a nitrogen atmosphere, the sintering temperature is 800 ℃, the time is 1h, and the heating rate is 3 ℃/min;
and (3) forming the flexible self-supporting iron-doped porous carbon nanofiber material and lithium metal into a half-cell, and plating lithium in the framework material by a deposition method to obtain the lithium metal battery composite cathode.
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